Lubricating compositions



United States Patent C) LUBRICATING COMPOSITIONS John Zachar, Berkeley, Calif., assignor to Shell Development Company, Emeryville, Calif a corporation of Delaware No Drawing. Application August 18, 1953, Serial No. 375,064

12 Claims. (Cl. 252-475) This invention relates to lubricants, and more particularly to lubricating compositions capable of inhibiting and even preventing wear. I

It is well known that chemical and mechanical wear is one of the most aggravating problems in the field of lubrication. From a practical point of view, wear may be considered as being of probably greatest importance. in lubrication, since the removal of metal necessitates replacement of parts. Although mechanical or abrasive wear, due to contacting of surfaces, is the most damaging, considerable amount of Wear is also due to chemical (corrosive) action. or due to a combination of chemical and abrasivewear. .These wear conditions are encoun tered in all types of engines and machines operating with all types of fuels, particularly high-sulfur fuels and under various conditions.

1 Because of the complexity of the problem, it is difficult topredict that a class of compounds, such as organic compounds containing phosphorus, halogen and/or sulfur (which compounds generally possess extreme pressure and friction reducing properties) would also possess anti-wear properties. Experience and accumulated knowledge in this field indicates that such might not be the case and that compounds possessing extreme pressure and friction reducing properties might be poor in preventing wear. i

It has now been discovered that improved lubricants can be obtained by incorporating into a base lubricant or into a lubricating composition a minor amount of a particular class of oil-soluble petroleum sulfonamides, preferably oil-soluble N-substituted sulfonamides derived from petroleum fractions rich in aromatics. By this is meant petroleum fractions containing from .1410 95% and preferably 19 to 50% of C4C4o alkyl aromatics, the predominant aromatics being monoaromatics although polyaromatics as well as mixtures of mono and polyaro- 2,748,682 Pa.tented May 29, 1956 ICC - converting the petroleum fractions to the sulfonamides matics can be present in the petroleum fraction in'minor amounts. Preferred petroleum fractions are those rich in Cm-Czo straight and/or branched chain alkyl substia tuted monoaromatics. q

Petroleum fractions particularly suitable forpreparing sulfonamides of this invention have the followingproperties:

Properties of base oils used for preparation ofjsulfon amides Viscosity Aromatics, Molec 011s cosity gfiff ig r wuliarm 5 8 absorption) 5 California Stocks: 1 1 r Motor Rafiinate 55-57 419 54 19 402 Industrial Raifinate 28-35 q. 37 West Texas Ellenburg- 25o Neutral 105 a0 7 464 380 Neutra1 101 457 62 39 1,534 Unextracted Heav Distillate 87 647 69 50 520 East Texas:

250 Neutral (10 pour point) 255 49 14 483 25 Intermediate I naturism--. s4 25 such as described in U. S. Patent 2,334,186. Among the preferred amines which can be used for converting petroleum fractions from their petroleum sulfonyl chlorides or fluorides state into corresponding petroleum sulfonamides of this invention include ammonia, ammonium hydroxide, primary and secondary and aliphatic amines, such as butyl, tertiarybutyl, isoamyl, 2-ethylhexyl, octyl, dodecyl, octadecyl, oleyl, stearylamines; methyl octyl, methyl dodecyl amines, etc.

Specific examples of sulfonamides of this invention include:

Petroleum a sulfonamide N-octadecyl petroleum sulfonamide N-Z-ethyl hexylpetroleum sulfonamide N-methyl, N-Octyl petroleum sulfonamide N-oleyl petroleum b sulfonamide The amount of petroleum sulfonamides of this invention which can be added to base lubricants may vary from about 0.5 to about 15% by weight and preferably in amounts of from about 0.5% to about 5% weight. Calculated on percent nitrogen the amount can vary from 0.05 to 5% nitrogen.

The base can be any natural or synthetic material havinglubricating properties. Thus, the base may be a hydrocarbon oil obtained from a paraftinic, naphthenic, Mid-Continent or Coastal stock and/or mixtures thereof. The viscosity of theseoils may vary over a wide range such as from SUS at 100 F. to 100 SUS at 210 F. The hydrocarbon oils may be blended with fixed oils such'as castor oil, lard oil and the like and/or with synthetic lubricants such as polymerized olefins, copolymers of alkylene glycols and alkylene oxides, organic esters, e. g., 2-ethylhe xyl sebacate, dioctyl phthalate, tn'octyl phosphate; polymeric tetrahydrofuran, polyalkyl silicone polymers, e. g., dimethyl silicone polymer and the like. If desired, the synthetic lubricants may be used as the sole base lubricant or admixed with fixed oils and derivatives thereof. In addition the base can be gasoline, ethyl fluids, fuel oil, greases, etc.

Compositions of this invention can be combined with other additives such as blooming agents, pour-point depressors, and/or viscosity improvers, anti-foaming agents, and the lik e. Among the specific additives for lubricating purposes which can be used are oil-soluble detergents which include oil-soluble salts of various bases with detergent-forming acids. Such bases include metalcontaining as well as organic bases. Metallic bases includev those of alkali metals, Ca, Mg, Cu, Sr, Ba, Zn, Cd, Al, Sn, Pb, Cr, Mn, Fe, Ni, Co, etc. Organic bases include various nitrogen bases as primary, secondary, tertiary amines and quaternary ammonium compounds, e. g., benzyl trimethyl ammonium hydroxide.

' Examples of detergent-forming acids are the fatty acids of say, 10 to 30 carbon atoms, tall-oil acids, rosin acids, wool-fat acids, paraffin-wax acids (produced by oxidation of paraffin wax), chlorinated fatty acids, aromatic hydroxy fatty acids, paraflin-wax benzoic acids, various alkyl salicylic acids, phthalic acid monoesters, aromatic keto acids, aromatic ether acids, diphenols such as di(alkylphenol) sulfides and disulfides, methylene bisalkyl phenols; sulfonic acids such as may be produced by treatment of alkyl aryl hydrocarbons or high-boiling petroleum oils with sulfuric acids; sulfuric acid monoesters; phosphoric, arsonic and antimony acid monoand Petroleum used was West Texas Ellenburger 250 N, 30% aromatics, I 7

di-esters, including the corresponding thiophosphoric arsonic acids and the like.

Additional detergents are the alkaline earth phosphate di-esters, including the thiophosphate di-esters; the alkaline earth diphenolates, specifically, the calcium and barium salts of diphenol monoand poly-sulfides.

Non-metallic detergents include compounds such as the phosphatides (lecithin and cephalin), certain fatty oils such as rapeseed oils, Voltolized fatty or mineral oils and the like.

An excellent detergent for the present purpose is the calcium salt of oil-soluble petroleum sulfonic acids. This may be present advantageously in the amount of about 0.025% to 0.2% sulfate ash. Also, alkaline metal salts of alkyl phenol-aldehyde condensation products are excellent detergents.

Antioxidants which are suitable for use in combination with the phosphono compounds comprise several types, for example, alkyl phenols such as 2,4,6-trimethylphenol, pentamethylphenol, 2,4-dimethyl-6-tertiary-butylphenol, 2,4-dimethyl-6-octylphenol, 2,6-dietertiary-butyl-4-methylphenol, 2,4,6-trietertiary-butylphenol, and the like; aminophenols such as benzylaminophenols; aromatic amines, such as N,N-dibtuyl-p-phenylenediamine, .diphenylamine, phenyl-beta-naphthylamine, phenyl-alphanaphthylamine, and dinaphthylamine.

Corrosion inhibitors or anti-rusting compounds may also be present, such as dicarboxylic acids of 16 or more carbon atoms; alkali metal and alkaline earth salts of sulfonic acids and fatty acids, organic compounds containing an acidic radical in close proximity to a nitrile, nitro, or nitroso group (e. g., alpha-cyanostearic acid), glycidyl phenyl ether, wax disulfide, etc.

Additional ingredients may comprise oil-soluble urea or thiourea derivatives, e. g., urethanes, allophanates, carbazides, carbazones, etc., polyisobutylene polymers, unsaturated polymerized esters of fatty acids and monohydric alcohols and other high-molecular-weight oil-soluble compounds.

Depending upon the additional additive used and conditions under which it is used, the amount of additive used may vary from 0.0 to 2% or higher. However, substantial improvement is obtained by using amounts ranging from 0.1 to 0.5% in combination with the primary additive of this invention.

Preferred compositions of this invention are illustrated by the following compositions:

Composition A Petroleum sulfonamide 0.5% N. Mineral lubricating oil Balance.

Composition B N-octadecyl petroleum sulfonamide 0.5% N.

Mineral lubricating oil Balance.

Composition C Composition F Petroleum sulfonamide 0.5% N.

Ca salt of oetyl phenol-formaldehyde 0.3% sulfate ash.

condensation product.

Mineral lubricating oil Balance.

4 Composition G Petroleum sulfonamide 0.5% N. Ca petroleum sulfonate 0.4% sulfate ash.

Ca salt of octyl phenol-formaldehyde 0.3% sulfate ash. condensation product.

Mineral lubricating oil Balance.

Composition H Petroleum sulfonamide 0.1% N.

Fuel oil Balance.

Composition I To illustrate the pronounced improvement obtained in preventing engine wear the following compositions were tested in a Fairbanks-Morse engine under the following test conditions and the results are recorded below:

Test conditions Speed R. P. M. 1200 Load H. P. 8 Test length, hr. 40 Oil temp., C.

Jacket temp., C. 100 Fuel, MIL-F-896 Class 11 Special 50 cetane Navy fuel.

When Compositions A and B were tested in the Fairbanks-Morse engine under the above conditions over 40% in wear reduction were noted when compared with a straight mineral lubricating oil base. On the other hand, lubricating oils containing organic-nitrogen compounds such as N-octadecyl diamylnaphthylsulfonamide caused an increase in wear of 40% over that of straight mineral oil while di-2-ethylhexyl amino phosphate (1% N) or urea (1% N) caused an increase in wear of 300% over that of the straight base oil.

Compositions of this invention in addition to being excellent anti-wear agents, possess good detergent and corrosion and oxidation inhibiting properties.

I claim as my invention:

1. A non-aqueous lubricating composition comprising a major amount of a mineral lubricating oil and from about 0.5 to about 15% by weight of an oil-soluble petroleum sulfonamide derived from a petroleum fraction rich in aromatics.

2. A non-aqueous lubricating composition comprising a major amount of a mineral lubricating oil and from about 0.5 to about 15 by weight of an oil-soluble N- substituted petroleum sulfonamide derived from a pctroleum fraction rich in aromatics.

3. A non-aqueous lubricating composition comprising a major amount of a mineral lubricating oil and from about 0.5 to about 15% by weight of an oil-soluble N- alkyl petroleum sulfonamide derived from a petroleum fraction rich in aromatics.

4. A non-aqueous lubricating composition comprising a major amount of a mineral lubricating oil and from about 0.5 to about 15 by weight of an oil-soluble N- octadecyl petroleum sulfonamide derived from a petroleum fraction rich in aromatics.

5. A non-aqueous lubricating composition comprising a major amount of a mineral lubricating oil and from about 0.5 to about 15% by weight of an oil-soluble N-2- ethylhexyl petroleum sulfonamide derived from a petroleum fraction rich in aromatics.

6. A non-aqueous lubricating composition comprising a major amount of a mineral lubricating oil and from about 0.5 to about 5% by weight of an oil-soluble petroleum sulfonamide derived from a petroleum fraction containing from 14 to of C4-C40 alkyl aromatics.

7. A non-aqueous lubricating composition comprising a major amount of a mineral lubricating oil and from about 0.5 to about 5% by weight of an oil-soluble N- substituted petroleum sulfonamide derived from a petroleum fraction containing from 14 to 95% of C4-C4: alkyl aromatics.

8. A non-aqueous lubricating composition comprising a major amount of a mineral lubricating oil and from about 0.5 to about 5% by weight of an oil-soluble N-alkyl petroleum sulfonamide derived from a petroleum fraction containing from 14 to 95% of C4-C4o alkyl aromatics.

9. A non-aqueous lubricating composition comprising a major amount of a mineral lubricating oil and from about 0.5 to about 5% by weight of an oil-soluble N- octadecyl petroleum sulfonamide derived from a petroleum fraction containing from 14 to 95% of C4-C4o alkyl aromatics.

10. A non-aqueous lubricating composition comprising a major amount of a mineral lubricating oil and from about 0.5 to about 5% by weight of an oil-soluble N-2- ethylhexyl petroleum sult'onamide derived from a petroleum fraction containing from 14 to 95 of C4 C4o alkyl aromatics.

11. A non-aqueous lubricating composition comprising a major amount of a mineral lubricating oil and from about 0.5 to about 5% by weight of an alkyl petroleum sulfonamide derived from a petroleum fraction containing from about 19 to of Clo-C20 alkyl substituted aromatics which aromatics are mixtures of mono and polyaromatic hydrocarbons.

12. A non-aqueous lubricating composition comprising a major amount of a mineral lubricating oil and from about 0.5 to about 5% by weight of an alkyl petroleum sulfonamide derived from a petroleum fraction containing from about 19 to 50% of Clo-C20 alkyl substituted monoaromatic hydrocarbons.

References Cited in the file of this patent UNITED STATES PATENTS Pings June 23, 1942 

1. A NON-AQUEOUS LUBRICATING COMPOSITION COMPRISING A MAJOR AMOUNT OF A MINERAL LUBRICATING OIL AND FROM ABOUT 0.5 TO ABOUT 15% BY WEIGHT OF AN OIL-SOLUBLE PETROLEUM SULFONAMIDE DERIVED FROM A PETROLEUM FRACTION RICH IN AROMATICS. 